Modifications of Tanabe-Sugano d⁶ Diagram Induced by Radical Ligand Field: Ab Initio Inspection of a Fe(II)-Verdazyl...

Quantum entanglement between the spin states of a metal center and radical ligands is suggested in an iron(II) [Fe(dipyvd)₂]²⁺ compound (dipyvd = 1-isopropyl-3,5-dipyridil-6-oxoverdazyl). Wave function ab initio (Difference Dedicated Configuration Interaction, DDCI) inspections were carried out to stress the versatility of local spin states. We named this phenomenon excited state spinmerism, in reference to our previous work (see Roseiro et al., ChemPhysChem 2022, e202200478) where we introduced the concept of spinmerism as an extension of mesomerism to spin degrees of freedom. The construction of localized molecular orbitals allows for a reading of the wave functions and projections onto the local spin states. The low-energy spectrum is well-depicted by a Heisenberg picture. A 60 cm^-1 ferromagnetic interaction is calculated between the radical ligands with the S_total = 0 and 1 states largely dominated by a local low-spin S_Fe = 0. In contrast, the higher-lying S_total = 2 states are superpositions of the local S_Fe = 1 (17%, 62%) and S_Fe = 2 (72%, 21%) spin states. Such mixing extends the traditional picture of a high-field d⁶ Tanabe-Sugano diagram. Even in the absence of spin-orbit coupling, the avoided crossing between different local spin states is triggered by the field generated by radical ligands. This puzzling scenario emerges from versatile local spin states in compounds which extend the traditional views in molecular magnetism.